Aldehyde condensation products of fluoroaliphatic phenols in skin protective compositions

ABSTRACT

CONDENSATION PRODUCTS OF ALDEHYDES AND FLUOROALIPHATIC PHENOLS ARE SUBSTANTIVE TO WOOL, SYNTHETIC POLYAMIDES, LEATHER AND SKIN, THE COMPOSITIONS PREFERABLY BEING EXTENDED WITH A SUITABLE PHARMACEUTICAL MEDIUM. THE CONDENSATION PRODUCTS ARE USEFUL FOR THE PREPARATION OF COMPOSITIONS THAT RENDER SUCH MATERIAL OIL AND WATER REPELLENT.

United States Patent 3,823,230 ALDEHYDE CONDENSATION PRODUCTS OF FLUOROALIPHATIC PI-IENOLS IN SKIN PROTECTIVE COMPOSITIONS Leland S. Endres, San Luis Obispo, Leo 'F. Gehlholf,

Village of Lake Elmo, and Dallas D. Zimmerman, Village of Shoreview, Minn., assignors to Minnesota Mining and Manufacturing Company, St. Paul, Minn.

No Drawing. Original application Oct. 29, 1970, Ser. No. 85,278, now abandoned. Divided and this application Sept. 21, 1971, Ser. No. 182,528

Int. Cl. A61k 27/00 US. Cl. 424-82 9 Claims ABSTRACT OF THE DISCLOSURE Condensation products of aldehydes and fiuoroaliphatic phenols are substantive to wool, synthetic polyamides, leather and skin, the compositions preferably being extended with a suitable pharmaceutical medium. The condensation products are useful for the preparation of compositions that render such materials oil and water repellent.

BACKGROUND OF THE INVENTION This is a division of application Ser. No. 85,278 filed Oct. 29, 1970, now abandoned.

The present invention relates to improved compositions and methods that render the skin repellent to oil and water and more particularly to certain novel compositions adapted to topical application to provide the skin with protection which is not readily removed by mild abrasion or hot detergent solutions.

It has long been known that the skin can be protected by the application of lotions, creams, and various other emollient compositions. These preparations are intended to exert a beautifying, softening and lubricating effect on the skin and may even contain medicinal ingredients. Other compositions have been described which will prevent absorption of harmful or cosmetically undesirable substances. However, the preparations heretofore known for the purpose described, while efiective to some degree, have all suffered from certain disadvantages. Mere emollients fail to protect the skin from exposure to injurious materials and only serve as palliative remedies afterwards. Barrier creams have been useful for certain specific conditions, but heretofore have failed to have broad general applicability. Furthermore, in maintaining personal hygiene, for example, by washing the hands, these compositions of the prior art are largely removed and repeated applications of the compositions are necessary. Obviously, the benefits obtained from these applications are not lasting since the protection is readily removed.

To provide skin protective compositions that resist removal from the skin by washing, particular ingredients have been incorporated into various compositions. For example, US. Pat. No. 2,727,846 teaches the incorporation of siloxanes into skin protective compositions. Such compositions, however, are easily transferred from the hands by touch or slight abrasion with other materials. This is a serious drawback in that even traces of such substances may bring about contamination of any surface touched. It is well known that the presence of even traces of silicones interfere with the action of adhesives, paints, and protective coatings. Furthermore, to be etfective on the skin, a coating of a siloxane must be applied which is virtually continuous. Such a coating adversely impairs access of air and transpiration of moisture which is needed for the well-being of the skin.

To overcome the disadvantages of siloxane-containing skin protective compositions, it is proposed in US. Pat. 3,100,180 that the siloxane be replaced by a minor 3,823,230 Patented July 9, 1974 amount of a fluorocarbon elastomer. In US. Pat. No. 3,470,292, it is proposed that the disadvantage of siloxane in skin protective compositions be overcome by incorporating a phosphatide such as lecithin, kephalin, and sphingomyelin. At present there is no known effective composition which adequately protects the skin from Water and oil known to applicants.

SUMMARY OF THE INVENTION According to the present invention, there is provided a method for protecting the skin against injurious and undesirable materials such as hydrous and oily materials. More particularly, there is provided compositions for the prevention of dish-pan hands that is caused by repeated immersion of the hands in hot water containing soap or detergents. Still more particularly, skin protective compositions are provided which are substantive to human and animal skin and that, by reason of this substantivity, afford long lasting protection of the skin to water and oil. The skin protection compositions of the present invention are adapted to topical application, are resistant to abrasion, and may include medicaments.

In accordance with the present invention, the skin is made both oleophobic and also resistant to aqueous materials, including acids and bases and also protected from irritating and otherwise undesirable substances, by applying thereto compositions comprising certain aldehyde condensation products of certain fiuoroaliphatic phenols in suitable pharmaceutical media as hereinafter defined. The compositions of the invention provide a long-lasting, indiscernible coating on the skin which is substantively bound to the skin and is not readily Washed or abraded from the skin as are other topical protective preparations described heretofore. Although extremely effective in its protective action, the coating apparently does not affect the transpiration of the skin. The term, substantive as used herein, means that the material has a high degree of tenacity for the skin and is essentially nonremovable by normal procedures. It is believed, though applicants do not intend to be bound thereby, that the compositions of the present invention are actually chemically bound to the skin at least to some extent.

Broadly speaking, compositions useful for the purpose of the invention are provided by incorporating a minor amount of aldehyde condensation product of a fluoroaliphatic phenol into a major amount of an aqueous pharmaceutically acceptable extending medium of the aqueous emulsion type which may also contain a thixotripic bodying agent or thickening agent. Preferably there is employed from about 0.3 to about 20 percent by weight of the condensation product. The term pharmaceutical extending medium as used herein includes such preparations as the bases for lotions, creams, ointments, and the like water-based preparations for topical application, which are sufficiently bodied so that the resultant composition is not watery or thin, but without limiting the viscosity or composition solely to a single type of preparation. For the purpose of the invention, the viscosity of the products described and claimed herein is required to be less than 1,000 centipoises when stirred at about 60 r.p.m. and may range upwardly to 1,000-5,000 centipoises, when determined using a Brookfield viscometer at about 25 C. The physical appearance of such preparations for topical application may range from that of a lotion through that of a flowable jelly, i.e., fairly stiff but flowable under mechanical force.

The aldehyde condensation products of certain fluoroaliphatic phenols that are disclosed herein are the significant and critical ingredient of the compositions of this invention. These condensation products are formed by the catalyzed reaction of an aldehyde with certain iluoroaliphatic phenols. The substantivity of these condensation products to human and animal skin and to other proteinaceous surfaces is believed to be obtained by reason of the phenolic hydroxyl group present in the condensation product. The oil and water repellent character is obtained by reason of the fluoroaliphatic group. Compounds possessing fluoroaliphatic groups have the greatest amount of substantivity if they possess at least two phenolic hydroxyl groups on separate aromtaic rings. Aromatic com pounds containing a fluoroaliphatic group and one or two hydroxyl groups on the same aromatic ring do not possess sufiicient substantivity to provide detergent resistance to the compound.

The aldehyde condensation products of fluoroaliphatic phenols that are preferred for the compositions of this invention are the acid catalyzed reaction products of the aldehyde and certain fluoroaliphatic phenols.

For purposes of this invention, an aldehyde is an organic compound having the formula ROHO wherein R is hydrogen or an organic radical having not more than seven carbon atoms, and which may be substituted by methyl, methoxy, ethyl, or ethoxy groups. More preferably, R is a lower alkyl group of the class C H where n is an integer of from 1 to 4. The aldehyde may be introduced into the reaction mixture either as a monomeric material or as the equivalent polymeric material which is convertible under condensation conditions to monomeric aldehyde. Suitable aldehydes (and materials capable of forming aldehydes) include acetaldehyde paraformaldehyde benzaldehyde paraldehyde butyraldehyde propionaldehyde furfuraldehyde tetrahydrofurfuraldehyde glutaralde'hyde trioxane glyoxal isobutylaldehyde The preferred aldehyde is formaldehyde.

For purposes of this invention, a fluoroaliphatic phenol is a compound that may be represented by the general formula in which I, m, p, and r, are each integers of l or 2; t is or 1; H is a hydrogen atom that is sufiiciently reactive to undergo a catalyzed condensation reaction with an aldehyde; A is an aryl nucleus of about 6 to 15 carbon atoms; OH is a phenolic hydroxyl group; R, is a monovalent fluorinated saturated non-aromatic aliphatic radical and Q is a divalent group linking A to R Examples of A include aromatic nuclei such as benzene, naphthalene, diphenyl and diphenylmethane and their alkyl, aryl, alkoxy, aryloxy, and halo derivatives.

Examples of Q include the following and combinations thereof:

In the above examples n is an integer from 1 to 15 and designates the number 'of carbon atoms in the alkylene or haloalkylene radical joining the R; group to the aryl group.

The fluoroaliphatic radical (ER:) is a monovalent fluorinated saturated non-aromatic aliphatic radical having at least 3 carbon atoms in the skeletal chain. This chain may 4 r j. be straight, branched or cyclic, and may be interrupted by divalent oxygen atoms or trivalent nitrogen atoms bonded only to carbon atoms. Preferably the chain does not contain more than one nitrogen atom or one oxygen atom for every two carbon atoms in the skeletal chain. A perfiuoroal-kyl radical is preferred, but an occasional hydrogen or chlorine atom may be present as substituents in the fiuorinated aliphatic radical provided that not more than one such non-fluorine substituent is present in such radical for every two carbon atoms, and that such radical contains a terminal perfiuoroalkyl group. Terminal in this connection refers to the position in the skeletal chain of the radical which is furthest removed from the group. Preferably, such a radical contains not more than a total of 20 carbon atoms whether r is 1 or .2 since such a large radical results in ineflicient use of the fluorine content.

Examples of fluoroaliphatic phenols suitable for the preparation of the aldehyde condensation products of the present invention are shown in Table I below.

TABLE I on on Q-o 0-081?" JO-CAFE OCH:

on on OH OH TABLE I-Continued OH OH (53 Oz----CIF17 (B-S Oz-Ca 11 1 INS Oa-CuFn $02 0 CaFn on 0H 0.0m" HP PCHPCiFfl The examples of phenols shown in Table I that may be employed to produce the aldehyde condensation products of this invention are prepared by the reaction of a perfiuoroalkyl sulfonyl fluoride, chloride or bromide with a suitable phenol having its hydroxy'(s) protected by acetylation or another method. The preparation of the perfluoroal kyl sulfonyl halides have been described in Brice eta 1., U.S. Pat. No. 2,732,398. The hydroxy aryl sulfonates shown in Table I may be prepared in accordance with the procedure given in Hansen, US. Pat. No. 3,346,612. The carbonyl compounds of Table I may be prepared by Friedel-Crafts reaction of perfluoroalkyl carbonyl chlorides, Ahlbrecht and Husted, US. Pat. No. 2,- 617,817 and phenols in a manner similar to that given in Beilstein, Organische Chemie, V01. VIII, p. 102 (1925). The perfl-uoroalkyl sulfonamides may be prepared by the reaction of the perfluoroalkyl sulfonyl chloride or bro mide with corresponding aminophenol in accordance with procedures given in Brice and Trott, US. Pat. No. 2,- 732,398.

The phenols of Table I where t is in the general formula of fluoroaliphatic phenols as heretfore described may be prepared according to the process given in Mattson, U.S. Pat. No. 3,326,928.

The pharmaceutical extending medium in the preferred embodiment of the present invention, consists essentially of an aqueous base which may contain th'ixotropic bodying agents or thickeners. In addition to water, the aqueous base may comprise alcohol or other solvents in amounts up to a few percent, usually not more than about percent by volume. The preferred bodying agent for the oil and water repellent composition of the invention is cetyl alcohol.

The pharmaceutical extending medium consists of all the various ingredients and adjuvants employed as a base except for the formaldehyde condensation product of certain perfluoroalkyl phenols which are added as an alcoholic solution or aqueous dispersion.

Illustrative of the types of materials which can be incorporated optionally in desired amounts for particular purposes are humectants, therapeutic ingredients, perfumes and colorants.-

The catalysts which may be used in the present invention are acid or base catalysts. Strong acids, such as sulfonic a'cids (sulfuric acid) or weak acids such as halogenated aliphatic acids (acetic acid) may be used to prepare novolaks. Preferred acids are trichloroacetic and para-toluene sulfonic acids. Of the many alkaline catalysts which may be used to prepare resoles, sodium hydroxide is preferred. Other catalysts include bases such as the hydroxide oxides and carbonates of lithium, sodium, potassium, cesium, magnesium, calcium, strontium, and barium and zinc oxide. Still other catalysts include ammonia, trimethyl amine, triethanolamine, and pyridine. The resins obtained from the base catalyzed condensations are called resoles.

As with most phenol aldehyde condensation reactions the character of the product obtained is very dependent on component reactivity, concentration and reaction conditions. It is thus difiicult to control the reaction in small scale preparations. In general, the effectiveness of acid catalysts decreases as follows: hydrochloric, nitric, sulfuric, trichloroacetic, oxalic, phosphoric, dichloroacetic, chloroacetic, formic, lactic, and acetic. Also, the more reative the phenol and aldehyde, the higher the molecular weight and hardness of the novolak obtained.

For the purposes of this invention, desirable condensation products are prepared using mole ratios of fluoroaliphatic phenol to aldehyde from 1.'1:0.3 to 10:35 or more. The preferred fiuoroaliphatic phenol to aldehyde ratios are 1.0206 to 1.0: l. 3. Reaction temperatures that may be used are from about 40 C. to about 150 C. or higher and the preferred reaction temperatures are from about 80 C. to about 110 C.

Desirable condensation products that possess oleophobic and hydrophobic properties are obtained when the perfluoroalkyl group of the phenol contains at least 3 carbon atoms up to more than 20 or more carbon atoms. Th preferred perfluoroalkyl groups are those containing from about 6 to about 10 carbon atoms.

The lower molecular weight condensation products, in general, are soft waxes having a buttery consistency. The novolaks prepared from 2- (2-chloro-3-perfluorooctyl)- n-propyl phenol and formaldehyde having an average molecular weight of about 800 to about 1500 are soft probably because they are not a precise reaction product but are mixtures of reaction products including unreacted phenol, phenol reacted with one or more aldehyde molecules, 2 phenol moieties reacted with one or more aldehydes, etc. It is these products that possess the greatest amount of substantivity to skin, leather, wool and polyamide surfaces. The higher molecular weight condensation products; i.e., those with molecular weights over about 1500, are hard, waxy solids and are useful in the preparation of oil and water repellent waxes and polishes. Other uses include coatings and molded products that have water and oil repellency and easy release" surfaces. Both the lower and higher molecular weigh-t condensation products are useful as a prepolymer to be extended with epoxy groups containing compounds and resins.

The molecular weight range of the soft waxy novolaks will, of course, vary depending upon the nature of the fiuoroaliphatic phenol, the aldehyde, the catalyst, the reaction temperature and the like. The use of a strong catalyst reduces the time and temperature required to prepare the product and vice versa.

The method for preparing the novel condensation products of the present invention comprises, generally, the steps of reacting a fiuoroaliphatic phenol having the formula' )1 )m[(Q)A H L as defined above with an aldehyde having the formula RCHO as defined above in the presence of a condensation catalyst at a temperature of from about /2 to 8 hours at a. temperature of from about 50 to 150 C.

The present invention will be more clearly understood with reference to the following non-limiting examples wherein all parts are by weight unless otherwise specified.

Example 1 Preparation of 2-(2'-chloro-3'-perfluorooctyl)-n-propyl phenol.--A 2-liter 3-neck flask equipped with a mechanical stirrer, a spanger tube and means for absorbing sulfur dioxide, and means for heating the flask, was charged with 225.6 grams of 2-allylphenyl acetate (1.45 moles) and heated to C. When the temperature reached 120 0., there was added 0.2 grams of benzoyl peroxide and, over a period of 2 hours, 755 grams (1.45 moles) of perfluorooctane sulfonyl chloride (b.p. 194 C.; 12 1.3200) was added while maintaining the temperature at 120 C. to C. To maintain a concentration of free radicals in the reaction mixture, there was added periodically during the two hours small portions of additional benzoyl peroxide (a total of 1.0 gram including the initial 0.2 grams were added). The mixture was heated at 120 an additional 30 minutes after the addition was complete. Then, without cooling, the flask was rigged for vacuum distillation. Vacuum was applied cautiously to avoid foaming and the mixture distilled. There was obtained 729.2 grams of 2-(2'-chloro-3'-perfluorooctyl-n-propyl)phenyl acetate (79.7% conversion) b.p. 140 C./0.40 mm. and unreacted o allylphenyl acetate. This compound is the precursor for the corresponding phenol.

Into a 10-liter flask equipped with a 2-foot distillation column and fractionation take-off head and means for heating the flask was placed 729.2 grams (1.16 moles) of 2-(2'-chloro-3'-perfluorooctyl)-n-propyl phenyl acetate, 7 liters of absolute alcohol and 1.0 gram of p-toluene sulfonic acid. The mixture was heated to reflux and over a period of 8 hours after which 4 liters of ethanol were removed by distillation. Of samples taken from the flask during this time, there was an indication of a continued decrease in acetate lgroup content as determined by infrared analysis. Distillation was continued to remove the remaining ethanol. The residue in the flask was purified by absorption on silica gel and elution with an 80:20 benzenezhexane solution. After removal-of the 'solvent by distillation, taking care not to overheat the product, 637.9 grams of 2-(2'-chloro-3'perfluorooctyl)-n-propyl phenol was obtained (99.5% of the theoretical amount). Melting point 69-73 C. E

Analysis-Calculated for C17H1oC1F170Z,C, 34-7 H, 1.7%; CI, 0.7%; F, 54.9. Found: C, 34.6%; H, 0; Cl,

I 9 1.79%; F, 54.8%. The above reactions are believed to be properly represented as follows:

10 tate, the isomeric mixture of 3- and -methy1-2-(2'-chloro- 3-per'fluorooctyl)-n-propyl phenyl acetate was prepared (b.p. 150 C./0.40 mm.) from which the isomeric mixture of 3- and S-methyl-Z-(2'-chloro-3'-perfluorooctyl)-npropyl phenols (wax-like material) was prepared. Anal- B110: 5 cH,-cn=cm elem-03F" ys1s.Calculated for CmH CIF O: C, 35.8%; H, 2.0%;

F, 53.7%. Found: C, 35.8%; H, 2.1%; F, 53.8%.

Example 4 0-00-0111 Additional W-perfluoroalkyl-propyl phenyl acetate and the phenols may be prepared therefrom, are given in om-orroi-om-cmu Table H.

TABLE II 0 dl wrfi 1- +l E 0H W-pertluoroalkyl-propyl acetate rigg i iilnfii pe uomalky 4-ehloro-2-(2-ehloro-3'-perfiuoro- 4-ehloro-2-(2-'chloro-3'-perfluoro- OH oetyD-n-propyl phenyl acetate oetyD-n-propyl phenol (M.P.

I (B.Pl50/.0.15 mm.). ass-93 0.

3,4,6-trlchloro-2-(2-chl0ro-3'-per- 3,4,6-trlehloro-2-(2'-ch1oro3-per- OHPCHCPCHPCJ" c% %TT1E? /3$tih fi.i .84 88 Pkwy 2,6-dleh1oro-2-(2-ehloro-3-per- 2,6-d1chloro-2-(2-ehloro-3-perfluorooctyD-n-propyl phenyl fiuorooetyD-n-propyl phenyl acetate (B.P. 160 0./0.05 mm.). (M.P. 88-89 Isomerlc mixture of 2,4- and 2,6- Isornerlc mixture of 2,4- and 2,6- 2 fi u fiffit'iiffiifirfitt' fifae tiltlfififiifitiittifit; Examp (B.P. 170 0 04 mix). y y By performing the procedures of Example 1, using in place of 2-allylphenyl acetate an isomeric mixture of 3- and S-chloro-Z-allyl phenyl acetates, the isomeric mixture The W-perfluoroalkyl-propyl acetates of Table II were of 3- and 5-chloro-2-(2'-ch1oro-3'-perfluorooctyl)-n-proprepared from 4-chloro-2-allyl-phenyl acetate, 3,4,6-tripyl phenyl acetate (b.p. 153 C./ 0.6 mm.) was prepared chloro-2-allyl-phenyl acetate, 2,6-dichloro-2-allyl acetate, from which the isomeric mixture of 3- and 5-chloro-2-(2'- and an isomeric mixture of 2,4- and 2,6-diacetoxy-allylchloro-3-perflu0rooctyl)-n-propyl phenols (yellow waxphenyl acetate respectively. like material) may be prepared. Analysis.-Calculated for Example 5 C H CI F O: C, 32.8%; H, 1.4%; F, 51.8%. Found: C, 33.2%; H, 1.6%; F, 51.8%, Table III gives the structure of yet other alkenyl-phenyl E 1 3 acetates that may be used to prepare additional W-perxamp e fluoroalkyl-phenols of this invention. These compounds When an isomeric mixture of 3- and 5-methyl-2-allyl also may be prepared by following the process of Examphenyl acetates is carried through according to the prople 1 using appropriate properties of W-perfluoro-alkyl cedures set out in Example 1 in place of 2-allylphenyl acesulfonyl halide and alkenyl phenyl acetate.

TABLE III Perfluoroalkyl Alkenyl phenyl acetates sull'onyl halide W-perfluoroalkyl alkyl phenol CAFISOzCl OH II Cl O-C-CH: 2}

CH: H-CHr-CrF.

CH1CH==CH:

Same as above CIFflSOZCl 011 C -CHrH-CH1C F D0. CaFuSOzCl 0H 01 @CHrH-CHr-Cdn D0 CrzFigSOaCl 0H (31 CHr-CH-CHz-CuFu TABLE IIIOontinued Perfluoroalkyl Alkanyl phenyl acetates sulfonyl halide W-perfluoroalkyl alkyl phenol CgFizSOsCl OH ll I O1 O-C-CHa I CHr-CH-CHr-CnFu C CH:

OH; I i

O CsFnSOzCl OH I CHz-CH-CHz-CaFn CH2CH= CH2 Same as above CaFnSOaCl 0H I :lCHrCHOHz-CgF 1 OH CnFiaSOaCl OH l ('31 l (Ill C 2CHCH:-CaFn @C r-C CHT-CGF1Q C F; CF:

OH C4F S02Cl OH Cl ('31 CHr-CH-CHrCdfi CHPCH-CH C Fg Br Br The alkenyl-phenyl acetates of Table III and those used in Examples 1 and 2 are prepared from the alkenylphenyl ethers which in turn are prepared from the phenols and alkenyl bromides. These reactions are well known procedures. See: J. Am. Chem. Soc., 72, 839-41 (1950); J. Org. Chem. 19, 726-32 (1956); J. Chem. Soc., Japan 57, 599-602 (1956).

For certain applications of the novel phenols of the present invention, it is desirable that there is no chlorine in the alkyl side chain of the W-perfluoroalkyl chloroalkyl phenol. The chlorine is readily removed by deyhdrogenation with a base such as for example, sodium hydroxide, to form a W-perfluoroalkyl alkenyl phenol and this compound can be hydrogenated to give the corresponding W-perfluoroalkyl alkyl phenol. Also, W-perfluoroalkyl alkyl phenols may be prepared by performing the dehydrochlorination and hydrogenation as in Example 6.

Example 6 An electrically heated rocking autoclave of 250 ml. capacity was charged with grams of 4-methyl-2-(2- chloro-3'-perfiuorooctyl)-n-propyl phenol (0.05 moles), 8.0 grams of potassium hydroxide, 10 ml. of water, 60 ml. of absolute alcohol and 6.0 grams of Raney nickel catalyst. Hydrogen was introduced at 3000 p.s.a. pressure and the autoclave was rocked for four hours while heating at 150 C. At the end of four hours the autoclave was cooled to about C., flushed with nitrogen and opened. The contents were removed and cautiously filtered hot (avoiding spontaneous ignition of the catalyst by keeping it wet at all times), and the catalyst was washed with several 50 ml. portions of hot ethanol. The combined filtrate and washings were stirred into about 250 ml. of water and acidified with dilute hydrochloric acid. The oily layer was separated and purified by absorption on silica gel in a column and elution with a benzene/hexane solvent. After vacuum distillation of the solvent there was obtained about 28 grams of 4-methyl- 2-(3'-perfluorooctyl)-n-propyl phenol.

In like manner other W-perfiuoroalkyl-alkyl phenols may be prepared from the corresponding W-perfiuoroalkyl-chloroalkyl-alkyl phenols, including those given in Table III.

The aldehyde condensation products of this invention may be prepared by the reaction of the perfluoroalkyl phenols disclosed above with aldehydes by well known procedures and in accordance with the following examples.

Example 7 Into a 500-ml. 3-neck resin flask equipped with mechanical stirrer, reflux column and thermometer, was placed 100 ml. toluene, 294.3 grams (0.50 moles) of 2-(2-chloro-3'-perfluorooctyl) n propyl phenol, 15.0 grams (0.50 moles) of paraformaldehyde and 30 grams of trichloroacetic acid. The mixture was stirred and heated at to C. for three hours and then at reflux C.) for an additional two hours. The solution was cooled to about 50 C., 40 ml. of cone. aqueous ammonia was added, and heat applied to reflux the mixture for an additional hour. The reaction mixture was cooled, washed several times with an equal volume of water, and the Example 8 Example 7 was repeated with the exception that 0.05 grams of p-toluenesulfonic acid was used as the condensation catalyst in place of 30 grams of trichloroacetic acid. A novolak was obtained that had a molecular weight by vapor phase osmometry of 1650. It was a tan-colored hard wax.

Example 9 Into a 500 ml. 3-neck resin flask equipped with a mechanical stirrer, reflux condenser and thermometer were placed 294.3 grams (0.50 moles) of 2-(2-chloro-3'-perfluorooctyl)-n-propyl phenol and 55 grams of formaldehyde (30% solution) (0.55 moles). The mixture was stirred and heated to 60 C. and made alkaline to phenolphthalein by dropwise addition of 20% sodium hydroxide in water. The mixture was then heated to 90 C. and stirred at this temperature for 4 hours. After this time,

the mixture was cooled to C. and acidified (pH: 6.0) with dilute phosphoric acid. The layers were allowed to separate and the yellow viscous lower layer removed from the flask. After drying in vacuum, a waxy yellow resin was obtained. This material is a resol and useful in further condensations to useful polymeric material. It is also useful for the preparation of protective compositions for the treatment of skin and leather.

Example 10 Table IV presents the repellency and substantive properties of a number of fiuoroaliphatic phenols and condensation products. It may be observed that, in general, monophenols and compounds with more than one O'H per carbocyclic ring exhibit only fair oil and detergent repellency on pigskin and are of less substantivity, i.e., little oil and detergent repellency remains after a detergent wash. Fluoroaliphatic phenol aldehyde condensation products having an average molecular weight of about 900 to about 1600 show good oil and water repellency on pigskin which is very similar to human skin and has the same properties for purposes of testing repellency. They also are substantive to the pigskin as is indicated by the fact that pigskins treated with these condensation products maintain their repellency after a 1-hour wash in a hot detergent solution.

TABLE IV.PROPERTIES OF FLUOROALIPHATIC PHENOLS AND CONDENSATION PRODUCTS Formaldehyde Repellency l (condensation Molecular Substan- Fluoroaliphatie Phenol catalyst) weight Water 011 tivity 1 OH None 590 Fair.. None.... None.

CHz-CHO1([3H:

aFu

2...::::::'::::: 0H .:.'...(10. 603 -..d0..... (10... D0.

CH2-CHC1JH1 CaFn 3..:::::::;::::: OH .:..-d0.=-...:......-: 624 .....do ..d0....- D0.

CHz-CHCl-?H2 4....';;.;.:..:::.'::: OH 693 .'..'d0 ..do..... Do.

Cl -CHr-CHCl-?Hz s n G1 5..-'..:::':;::::: OH -d0..-:.-.-.-.'.' 606 -..d0.... Fair..... D0.

OH:OHC1(|JH2 Ca 11 OH 6.51:3:325: OH ':.---d0.-...::.:-: 622 .'..d0.....:'..d0-.... D0.

CHr-CHCl-CH:

3F" HO OH 7....:7.::..:: OH 630 None.... GOOd... D0.

TABLE IV-Contlnued Formaldehyde Repelleney 8 (condensation Molecular Substan- Fluoroaliphatic Phenol catalyst) weight Water Oil tivlty h 8 011 ....None. 624 Fain... None None:

I s n CHrCHCl-HI 9 03 Plus novolsc ot 300 ...do n

011 CH:CHCl-CH:

sFu

1o ()H 0310' 1,100 Good. c 11 Good,

CH:-CHC1(3H:

11 Same as above mm 1) d0 CHzO 12 rln (EH 14 (|)H 2 o ..d0 Fair CHzCHC1CH:

15 0H CHaO' 1,150 ---d0 --d0. Do.

. OSOzCgFr! 16 0H 11 1,218 ...do ..do... Good.

(I3H,CHC1CH CH:- CH CHCl-OH, CaFi1 aFn H: CH:

17 OH C1110 3,000 Falr...-- Falr Poor.

CHr-CHCl-CH: v laFu I Test on the phenol before reaction with aldehyde.

b Molecular weight determined by vapor phase osmometry. v Condensation catalyst is trichloroacetic acid.

6 Condensation catalyst is p-toluenesulionic acid.

a Test on the dihydroxy-diphenyl methane.

1 Molecular weight of the non-perfluorinated novolac.

lAiter application of an 8% solution to raw pigskin that had been extracted with tetrahydroiurane, dried, and rehydrated to a flexible condition. h Repellency of treated pigskin after it has been given a 1-hour wash with a 0.5% aqueous solution 0! sodium dodecylbenzene sulionate at C.

If the perfluorooctyl group of the compounds and products of Table IV are replaced by other perfluoro groups including perfluorobutyl, perfluoroamyl, perfluorohexyl, perfluorododecyl, pcrfluorodecyl, and other perfluoroalkyl groups, corresponding compounds and products are obtained that have properties similar to those listed in Table IV.

If the formaldehyde used in the condensation products of Table IV is replaced by other aldehydes including acetaldehyde, benzaldehyde, butyraldehyde, furfuraldehyde, glutaraldehyde, glyoxal, paraldehyde, propionaldehyde, tetrahydrofurfuraldehyde, and other aldehydes desirable condensation products are also obtained that have properties similar to those listed in Table IV.

The following example demonstrates a preferred application of the condensation products of this invention in a composition that provides effective protection of the skin against aqueous and oily material that otherwise might injure the skin.

Example 11 To prepare a perfumed protective handcream, an aque- 1 9 ester of p-hydroxybenzoic acid, an oil soluble bactericide) and 0.004 parts of propyl gallate (antioxidant) was also heated to 50 C. was slowly added to the aqueous mixture, the entire mixture was thoroughly mixed and while mixing, cooled to 32 C., then 0.10 parts of perfume Flueroma Fragrance No. 9006 available from U.O.P. Fragrances Division of Universal Oil Products, Inc., New York, was added. After the creamy emulsion is cooled to below about 30 C. while mixing, it is discharged from the mixer.

The emulsion was then rubbed onto the hands in the usual manner and was found to be protective against water, oil and detergents.

Handcreams with similar desirable properties may be prepared by using in accordance with Example 11 from 0.5 to 4 parts of cetyl alcohol per 100 parts of handcream. Less cetyl alcohol than 0.5 parts gives thin unstable emulsions and more than 4 parts of cetyl alcohol reduces the oil repellency of the handcream. Likewise, the preferred concentration of perfume or fragrance depends on' the type of fragrance used. In general, a useful concentration is from about 0.05 parts up to 0.15 parts per 100 parts of handcream. Less than 0.05 parts of fragrance is inelfective and more than 0.15 may reduce the oil repellency of the handcream. Also, handcreams with desirable properties may be prepared by using in accordance with Example 4 from 0.2 to about 0.4' parts of ammonium lauryl sulfate.

treated with the test formulation as prepared in Example l1, permitted to dry after which a droplet of soap solution (0.5% sodium lauryl sulfonate in deionized water) or oil (75% mineral oil of 310 to 320 Saybolt-secends in heptane) was placed on the surface from a syringe. Pictures taken level with the treated surface at times of 0, 15, 30, 60 and 3-00 seconds were used to determine the wetting rates of these potential irritants. Initial contact angle as well as rate of change of contact angles were usedto compare repellencies of formulations. Substantivity is measured by determining the contact angle of the mineral oil-heptane mixture on the treated callus tissue or pigskin after it is subjected to a minute wash with a 0.5% solution of sodium lauryl sulfonate at C., rinsed with Warm water and dried.

It may be seen by inspection of Table V that the creams and lotions made using novolaks of 2-(2'-chloro- 3'-perfluorooctyl)-n-propyl phenol exhibit oil and soap repellency and that this condensation product is substantive to callus tissue. These results are indicated by the high contact angle of drops of oil on treated callus tissue after it has been washed in hot detergent solution. Creams and lotions made with other novolaks and aldehyde condensation products having an average molecular weight of from about 900 to about 1600 in accordance with the teaching of this invention are repellent to aqueous and oily substances and are substantive to skin and proteinaceous materials.

TABLE V.REPELLENCY TESTS ON CALLUS TISSUE Droplet contact angle, degree Before detergent wash After detergent wash Preparation of Preparation oi Preparation of- Elapsed Untreated Example 11 Example 12 Untreated Example Example Oil Soap Oil Soap Oil Soap oil 11, oil 12, oil

28 76 89 97 84 101 10 78 75 20 51 82 96 82 99 74 72 15 43 so 93 7s 96 as 10 27 78 93 76 95 63 64 10 10 78 72 75 84 47 52 l Wets out almost immediately.

The cream of Example 11 was the result of the study Example 14 of many formulations to find composites that do not have components that interfere with the substantivity of condensation products of the invention. In general, inorganic thickeners, fugitive surfactants, fluorochemica-l surfactants, fatty acids, most common surfactants and most fatty alcohols are to be avoided because rather large quantities of these materials are required to achieve emulsion stability. At the high concentration of these materials required the substantivity and repellency of the condensation products of this invention are reduced.

Example 12 A protective lotion was prepared by dissolving 0.004 parts of propyl gallate, 4 parts of thenovolak of 2-(2'- chloro-3-perfluorooctyl)-n-propylphenol (prepared as in Example 1) and 0.1 part of perfume in 96 parts of denatured ethyl alcohol. The resulting lotion provided protection of the hands against hot soapy water. When applied to the hands and other parts of the body, the cream pro vided protection against aqueous and oily solutions. In place of denatured ethyl alcohol, isopropanol or a Freon or a mixture of one of more Freons having a boiling point of about 70 F. to about 150 F. may be used. If the 10- tion is to be used to treat leather, textiles, or synthetic materials, then other solvents may be used including diethyl ether, acetone, methyl ethyl kctone, amyl acetate, benzene, chlorinated hydrocarbons and the like.

Example 13 The repellency and substantive properties of the protective compositions of this invention were determined by photographically measuring droplet contact angles over a five minute period. Pigskin or callus tissue was An aerosol spray embodying the compositions of the invention is prepared by charging a 6 ounce aerosol can with grams of a 4% solution of the novolak of 2-(2'- chloro-3'-perfluorooctyl) n-propyl phenol (prepared as in Example 7) in ethanol and 90 grams of a 40:60 mixture of Freon 11 and Freon 12. To disperse the protec tive composition, the aerosol can is equipped with a Precision valve and dip tube. When sprayed on the hands or other parts of the body, a pleasant emollient character is noted and the hands and body are aiforded protec tion against oil and aqueous based irritants, acid and basic solutions even after the hands and body are washed in water or detergent solutions.

What is claimed is:

1. A skin protective composition which is substantive to the skin and is for protecting the skin from aqueous and oil compositions, comprising:

a condensation product of the catalyzed reaction of a perfluoroaliphatic phenol having the formula wherein l, m, and r are integers of 1 or 2; p is 1; tis 0 or 1; H is a hydrbgen atom sufiiciently reactive to undergo a catalyzed reaction with an aldehyde;'A is an aryl nucleus of from 6 to 15 carbon atoms; OH is a phenolic hydroxyl group; R; is a monovalent fluorinated saturated aliphatic radical containing from 3 to 20 carbon atoms; and Q is a divalent group linking A to R and is selected from the class consisting of alkylene, alkenylene, haloalkylene, sulfonate, sulfonyl, sulfonamide, carbonyl, carbonamide, and

21 oxaalkylene with an aldehyde selected from the group consisting of an aldehyde having the formula RCHO wherein R is hydrogen or a lower alkyl having the formula C H wherein n is an integer of from 1 to 4, benzaldehyde, furfuraldehyde, glutaraldehyde, glyoxal, paraformaldehyde, paraldehyde, tetrahydrofurfuraldehyde and trioxane, said condensation product having a molecular weight of from about 800 to about 1500; and

an aqueous pharmaceutically acceptable extending medium for holding said condensation product which medium is compatible with said condensation prodnot, said condensation product comprising about 0.3 to about 20 percent by weight of said composition.

2. The composition of Claim 1 wherein said aldehyde is formaldehyde and said phenol is 2-(2-chloro-3'-perfluorooctyl) -n-propyl phenol.

3. The composition of Claim 1 wherein the aryl nucleus of from 6 to 15 carbon atoms is selected from the group consisting of benzene, napthalene, diphenyl, diphenylmethane and the alkyl, aryl, alkoxy, aryloxy and halo derivatives thereof.

4. The composition of Claim 3 wherein the aryl nucleus is benzene.

5. The composition of Claim 4 wherein the aldehyde has the formula RCI-IO and where R is hydrogen.

6. The composition of Claim 4 wherein Q is haloalkylene having the formula (C H Cl) wherein n is an integer from 1 to 15.

7. The composition of Claim 6 wherein the aldehyde is paraformaldehyde.

8. The composition of Claim 7 comprising about 3 to 15 parts by weight of said condensation product, about 0.5 to 4 parts by weight cetyl alcohol, about 0.2 to 0.4 parts by weight ammonium lauryl sulfate and about 0.05 to 0.15 parts by weight of an oil soluble perfume in from about to parts by weight water.

9. The composition of Claim 7 comprising about 3 to 15 parts by weight of said condensation product, about 0.5 to 4.0 parts by weight cetyl alcohol, about 0.2 to 0.4 parts by weight sodium lauryl sulfonate and about 0.2 parts by weight of an oil soluble perfume in from about 80 to 95 parts by weight water.

References Cited UNITED STATES PATENTS 2,049,447 8/1936 Hanel et a1. 260-619 R 3,151,096 9/1964 Kordzinski 260619 R STANLEY I. FRIEDMAN, Primary Examiner US. Cl. X.R.

260-619 A, 619 R, 623, 623 R 

